Nanocomposite gel polymer electrolyte (GPE) films based on poly(poly[ethylene glycol] methyl ether methacrylate)/graphene oxide (GO) (P[PEGMA-GO]) have been prepared by in situ conventional free radical polymerization (FRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization as controlled radical polymerization (CRP) using 2-cyano-2-propyl dodecyl trithiocarbonate (CPDT) as RAFT agent. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) showed that prepared nanocomposite films had amorphous structure and also, thermogravimetric analysis (TGA) showed appropriate thermal stability of samples. GPEs prepared via FRP showed slight higher ionic conductivity that GPEs prepared via RAFT polymerization. In both synthetic approaches, an optimum GO amount of 0.3 wt. % was obtained considering ionic conductivity. At ambient temperature, P(PEGMA-GO) with 0.3 wt. % GO prepared via FRP indicated the highest ionic conductivity of 4.05 × 10−3 S cm−1, a satisfactory lithium ion transference number (t+) of 0.6, and the excellent interface compatibility with electrodes. The lithium ion battery with P(PEGMA-GO0.3%) as GPE also exhibited electrochemical stability window up to 4.6 V vs. Li/Li+, a high charge-discharge capacity of 179 mAh g−1 at 0.1 C, and capacity retention of 91% after 100 cycles.